DE4426186A1 - Glycol ether-containing aminotriazine derivatives and their use in coating resins - Google Patents

Abstract

The invention concerns binders containing: A) an aminotriazine derivative in which the triazine primary amino groups are methylolated on average with at least one mol of formaldehyde per mole of primary amino groups and these methylol groups are etherified on average with at least 0.5 mole primary alcohol per mole of methylol group, and the primary alcohols are a mixture containing: a) 0.5 to 99.5 mol % of a C1-C4 alkanol and b) 99.5 to 0.5 mol % of an alcohol of the formula (I) R<1>-O-[R<2>-O]n-R<3>-OH, in which R<1> stands for a C1-C24 alkyl group or a C6-C12 aryl group which may optionally be substituted by one to three C1-C8 alkyl groups, and R<2> and R<3>, independently of each other, stand for a C2-C8 alkylene group, and n means an integer from 1 to 100, or a mixture of higher-boiling alcohols having a boiling point of more than 120 DEG C at 1 bar, which contains at least 10 mol %, relative to the higher-boiling alcohols, of alcohols of formula I; and B) a radical polymer, which can be crosslinked with the aminotriazine derivative, a polycondensate or polymer additive.

Description

The invention relates to binders containing

• A) an aminotriazine derivative in which the primary amino groups of the triazine are methylolated on average with at least one mole of formaldehyde per mole of primary amino groups and these methylol groups are etherified on average with at least 0.5 mole of primary alcohol per mole of methylol group, and the primary alcohols containing a mixture
  • a) 0.5-99.5 mol% of a C₁-C₄ alkanol and
  • b) 99.5-0.5 mol% of an alcohol of the formula R¹-O- [R²-O] _n -R³-OH (I), wherein R¹ is a C₁-C₂₄-alkyl group or a C₆-C₁₂-aryl group , which can optionally be substituted by one to three C₁-C₄-alkyl groups and, R² and R³ independently represent a C₂-C₄-alkylene group and n is an integer from 1-100, or a mixture of higher-boiling alcohols with a Boiling point above 120 ° C at 1 bar, which contains at least 10 mol%, based on the higher-boiling alcohols, alcohols of the formula I, and
• B) a radical which can be crosslinked with the aminotriazine derivative Polymer, polycondensate or polyadduct.

The invention further relates to an aminotriazine derivative in which the primary amino groups of the triazine on average with at least one mole of formaldehyde per mole of primary amino groups methylolated and these methylol groups on average with at least 0.5 mol primary rem alcohol are etherified per mole of methylol group, and it the primary alcohol is a mixture containing

• a) 50-99.5 mol% of a C₁-C₄ alkanol and
• b) 0.5-50 mol% of an alcohol of formula I above or one Mixture of higher boiling alcohols with a boiling point above 12 ° C at 1 bar, which is at least 10 mol%, based  to the higher-boiling alcohols, alcohols of the formula I ent holds.

Highly methylated and largely with short-chain alcohols etherified aminotriazines, especially melamine, are considered Crosslinker for polymers containing hydroxyl groups in lacquer binders used.

A high degree of alkylation and etherification compared to amino triazine derivatives with high proportions of free NH and OH groups results in a lower solution viscosity. This enables the Manufacture of medium and especially high-solids paints. The like coating agents with reduced volatile content Solvents are preferred for ecological reasons (ge lower organic C emission) and offer the paint user costs advantages (less effort in solvent processing or combustion). At the same time, however, the high Partial degree of alkylation and etherification methylolated and partially etherified aminotriazine derivatives ver reduced reactivity when crosslinking OH groups Lacquer binders.

The lower reactivity can only be achieved with a higher branding temperatures with the disadvantage of higher energy consumption and Yellowing of the painted surfaces or by increased addition of acidic catalysts, acids and / or their amine salts with the disadvantage of reduced weather resistance (hydro phile acid remains in the paint) balance.

From DE-A 24 14 426 are with ethylene glycol monoethyl ether etherified methylolaminotriazines and their use as Crosslinkers for hydroxyl-containing polymers are known.

The reactivity of these aminotriazine derivatives for crosslinking with However, hydroxyl groups are not yet sufficient.

DE-A 36 32 587 describes melamine-formaldehyde resins ben which with glycol ethers, e.g. B. also polyethylene glycol, are etherified. In addition to the glycol ethers, other alcohols can also be used hole can be used for etherification. Glycol ethers are in the Mixtures, however, always in a clear excess. The Resins are formed by the simultaneous implementation of melamine aldehyde and glycol ethers prepared, the implementation Weitge without water, i.e. using paraformaldehyde to be led.

The object of the present invention was amino Manufacture triazine derivatives, which due to their low Solution viscosity for the production of low-solvent paints are suitable and compared to the usual resins such. B. Hexa methoximethylmelamine resins, a significantly increased reactivity with Have OH group-containing binders.

Furthermore, good elasticity, good tolerance of the Aminotriazine derivatives with the other components of bindemite teln, z. B. for paints, as well as good application properties binders containing the aminotriazine derivatives, wanted.

The aminotriazine derivatives A) described above are are at least partially methylolated and etherified amino triazine.

Suitable aminotriazines are, for. B. melamine, benzoguanamine, Acetoguanamine and bisguanamines such as adipo-, glutaro- or methyl glutarobisguanamine and spiroguanamine. Also come into consideration Connections which have several, e.g. B. condensed aminotriazine contain cores.

Preferred are melamine and compounds which have several melamines cores, e.g. B. 2 to 5 melamines bridged via methylol groups ent hold, or their mixtures. Such mixtures of melamines and Highly condensed melamine resins preferably contain at least at least 40 mol% melamine. Melamine is particularly preferred.

The aminotriazines are preferred on average with at least 1 mole as at least 1.4 mol, particularly preferably with at least 1.7 moles of formaldehyde methylolated per mole of primary amino groups and these methylol groups on average with at least 0.5 mol preferably at least 0.6 mol and particularly preferably with at least one at least 0.7 moles of a mixture of primary alcohols per mole Etherified methylol group.

This mixture contains

• a) 0.5 to 99.5, preferably 50 to 99.5, particularly preferably 85 up to 99.5 and very particularly 90 to 99 mol%, based on the Mixture, a C₁-C₄ alkanol and
• b) 99.5 to 0.5, preferably 50 to 0.5, particularly preferably 15 up to 0.5 and very particularly preferably 10 to 1 mol%, based on the mixture, an alcohol of formula I or above a mixture of higher boiling alcohols with one boil  point above 120 ° C at 1 bar, which is at least 10 mol%, preferably at least 30 mol%, particularly preferably minde contains at least 60 mol% of an alcohol of formula I.

Suitable C₁-C₄ alkanols are all with a boiling point below 120 ° C at 1 bar, preferably methanol, i-butanol or n-butanol and Mixtures of such alkanols.

Preferred alcohols of the formula I are those in which R¹ is a C₁-C₂₄-, particularly preferably for a C₁-C₆ alkyl group stands, R² and R³ independently of one another for a C₂-C₄-, especially preferably a C₂-C₄ alkylene group and very particularly preferably R² and R³ is an ethylene group and n is an integer of 1 to 20, particularly preferably from 1 to 5.

As alkanols of the formula I may be mentioned, for. B. Di-, Tri- or Te traethylene glycol monomethyl ether, or the corresponding mono butyl ether.

Higher boiling alcohols with a boiling point <120 ° C at 1 bar, which are used in a mixture with the alcohols of the formula I. that can, are preferably those with up to 20 carbon atoms and without further heteroatoms. May be mentioned for. B. n-pentanol, 2-pentanol, cyclopentanol, 2-methylbutanol, 3-methyl-1-butanol, Cyclohexanol, 4-methyl-2-pentanol, methylcyclohexanol, hexahydro benzyl alcohol, 2, 4-dimethyl-3-pentanol, 2-ethylhexanol, nonanol, Decanol, oxo and fatty alcohols with chain lengths from C₁₂ to C₂₀ like Lauryl alcohol, tridecanol, myristyl alcohol, cetyl alcohol, Stearyl alcohol or oleyl alcohol, aromatic alcohols such as benzyl alcohol, o-, m- or p-methylbenzyl alcohol, 1-phenyl ethanol, 2-phenylethanol, α-ethylbenzyl alcohol, α-isopropyl benzyl alcohol, hydroxymethylnaphthalene, 1- (α-hydroxyethyl) - naphthalene.

The aminotriazine derivatives A) are preferably prepared by transacetalization of aminotriazines, which accordingly of the above-mentioned degree of methylolation or of the above Degree of etherification methylolated and exclusively with the C₁-C₄ alkanols a) are etherified. These are used for reetherification Aminotriazine derivatives added to alcohols b). The alcohols b) are possibly only in a slight excess, based on the desired content of these alcohols in the aminotriazine derivative puts.

The transacetalization is usually carried out without the addition of solvents carried out. In principle, the addition of solvents possible, it is preferably either the im  Starting product bound alcohol a), for example Methanol, ethanol, n- or iso-butanol, or around aprotic solvents medium the under the reaction conditions not with the use can react to substances. Such solvents are listed below whose ethers such as, for example, diethyl ether, diisopropyl ether, Methyl tert-butyl ether, tetrahydrofuran, dioxane and 1,2-di methoxyethane, aromatic solvents such as benzene, Toluene, xylene and isopropylbenzene or halogenated hydrocarbon substances such as di-, tri- and carbon tetrachloride, di-, Tri- and tetrachloroethane and chlorobenzene.

The reaction is preferably carried out with acid catalysis with or ganic and / or inorganic acids in water at 25 ° C have a pK value <4, for example citric acid, wine acid, lactic acid, chloroacetic acid, trichloroacetic acid, ants acid, oxalic acid, malonic acid, maleic acid, fumaric acid, phthal acid, o-nitrobenzoic acid, o-chlorobenzoic acid, methanesulfonic acid, Benzenesulfonic acid, p-toluenesulfonic acid, naphthalenesulfonic acid, Hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid. Likewise Lewis acids such as boron trifluoride or are suitable Aluminum chloride.

The reaction is generally carried out at temperatures from 40 to 150 ° C, preferably at 60 to 120 ° C and at normal pressure or at carried out under reduced pressure. By working at vermin dertem pressure z. B. from 1.5 to 500 mbar, preferably from 10 to 200 mbar, volatile components of the Reaction mixture, mainly that bound in the starting product Alcohol a) distilled off, the reaction equilibrium towards of the products postponed and high sales of alcohols b) achieved will.

After reaching the desired conversion of at least 60%, preferably 80%, based on the used Alcohols b), measured by the decrease in alcohols b) or by the Increase in the alcohol released a) by lowering the Temperature and, if necessary, neutralization of the catalyst set acid with bases such as aqueous or alcohol caustic soda or caustic potash, with alkylamines such as triethyl amine, tri-n-propylamine, tributylamine, tri-2-ethylhexylamine, Dimethylethylamine or alkanolamines such as diethanolamine, tri ethanolamine, triisopropanolamine, dimethylethanolamine, diethyl ethanolamine, dibutylethanolamine, methyldiethanolamine or butyl diethanolamine ended.  

The transacetalizations can be carried out in one or more stages leads. In the case of alcohol mixtures b) the reaction e.g. B. first with an alcohol up to a turnover of min carried out at least 60% then optionally further acid than Added catalyst and the remaining alcohol or alcohols and the reaction will continue.

After the reaction has ended, another may be carried out Distillation at reduced pressure from 5 to 200 mbar and at ge if necessary, elevated temperature of 40 to 140 ° C to residual amounts largely remove volatile components. You get clear, colorless to slightly colored resins with a viscosity of preferably 0.5 to 20 Pa · s (at 23 ° C) and a content of unreacted alcohol b) preferably below 20 wt .-%, ins especially less than 10% by weight, particularly preferably less than 5% by weight.

If desired, the resins can also contain solvents Dilution can be added.

In addition to the aminotriazine, the binder according to the invention contains derivative A) a radical polymer, polycondensate or Polyadduct B), which with the aminotriazine derivative, for. B. by contains active hydrogen atoms (OH; NH, SH groups) can be networked.

As component B) z. B. alkyd resins, polyester resins, Epoxy resins, polyurethane resins, radical polymers based on of acrylates, vinyl esters, dienes and vinyl aromatics or their Mixtures.

Radical polymers, polycondensates or are preferred Polyadducts with OH groups, preferably with a hydroxyl number from 20 to 200 mg KOH / g substance (according to DIN 53240).

The binders of the invention can, for. B. 1 to 99, preferred example 1 to 40, particularly preferably 5 to 30 wt .-% of the amino triazine derivatives A) and 1 to 99, preferably 60 to 99 and be particularly preferably 70 to 95% by weight, component B), based on the sum of A) and B).

The binders can e.g. B. in the form of solutions in water or organic solvents or in the form of aqueous dispersions available.  

The binders can be used for the intended purpose The usual auxiliaries are added, e.g. B. Rheology Aid medium, leveling agents, defoamers, pigments, dyes etc.

The binders are particularly suitable for coatings, ins especially as paint binders.

They are suitable for a wide variety of substrates, e.g. B. Glass, plastic, metal or wood.

The coatings can be applied by the usual application methods e.g. B. by brushing, dipping, rolling, knife coating or spraying be worn.

The binders according to the invention are distinguished by high ver wetting reactivity from both thermal hardening (Ein firing lacquers) as well as in acid catalysis (acid-curing lacquers) allow significantly shorter reaction times than known full alky gated amino resins, such as those used as a starting material were used for the etherification.

Suitable catalysts for acid catalysis are, for. B. strong Acids such as sulfonic acids (e.g. para-toluenesulfonic acid, Naphthalenesulfonic acid etc.), phosphoric acid or derivatives of Phosphoric acid, hydrochloric acid or other mineral acids are used. It can also metal salts such. B. zinc nitrate can be used.

Amine salts of the acids mentioned, for. B. p-toluenesulfonic acid and triethanolamine, the components can also be added individually, or commercially available amine salts e.g. B. Nacure® types.

The aminotriazine derivatives according to the invention are suitable special also as the sole binder, e.g. B. for coating of furniture finish foils. You can use the Addi mentioned above tive, but especially plasticizers and catalysts, for. B. Poly alkylene glycols and arylsulfonic acids, for curing, more common wise at high temperatures.

Examples

Unless otherwise stated, all percentages are by weight percent.

The commercially available He usually used as preliminary products xamethoximethylmelamine (HMMM) resins are mixtures of ver different, e.g. T. also containing several melamine seeds  Connections represent. For this reason, they are at temperatures below 46 ° C, the melting point of HMMM, liquid. Of course can also use pure, crystalline HMMM as a starting material used, the transacetalization usually leads to liquid products. For the calculation of the reaction approaches was used for the HMMM resins used as an average molecular weight of 390 g / Mole, the molar mass used by HMMM.

The glycol ethers too, especially with a higher number of Ethylene oxide units, molecular weight distributions. Also here the molecular weight is calculated from the average number on bound ethylene oxide units.

The catalyst p-toluenesulfonic acid is always included as a monohydrate the molar mass used 190.22 g / mol.

1. Test and analysis methods

Free formaldehyde
Determination by the titrimetric sulfite method according to DIN 16746-A.

Total formaldehyde
Titrimetric after acid digestion.

Alcohol and glycol ether, free
Determination by gas chromatography.

Alcohol, bound
Difference between the total chromatographic alcohol content found after acidic conclusion and the free alcohol content.

Non-volatile components / solids content
In accordance with DIN 53216, 2 g of resin and 2 g of butanol are weighed onto a dry content sheet, baked in a convection oven at 125 ° C for two hours, then weighed out and the non-volatile content in% by weight (baking residue) calculated.

viscosity
The viscosity of the resins is determined using a cone-plate viscometer, VISKO-PLOT from Epprecht Instruments + Controls AG, CH5606 Dottikon.

2. Transacetalization Products General preparation instructions for Examples 1 to 16

In an apparatus suitable for vacuum distillation with Stirrer, cooler and distillation receiver are 1.5 mol one Hexamethoximethylmelaminharzes with the in the examples of Amount of glycol ether specified in Table 1, possibly with further high-boiling alcohols and with the amount mentioned p-Toluenesulfonic acid (pTSS) is added as a catalyst and on the specified temperature warmed. After reaching the Temperature is distilled for one hour at the specified pressure and with one of the amounts of acid used Amount of tributylamine neutralized. After neutralization is heated to 110 ° C and another 15 minutes at reduced distilled pressure, if necessary with the specified amount of Diluted 1-methoxypropanol-2 and abge to room temperature cools. After filtration, clear, colorless or pale yellow colored resins that are stable for at least 6 months are, d. H. have no phase separation and can be processed stay. The analytical data are summarized in Table 2 composed.

General preparation instructions for Examples 17 to 20 and for Comparative Example 1

1.5 mol of a Hexamethoximethylmelaminharzes in a, with Stirrer, cooler and distillation template provided for Vacuum distillation suitable equipment, with 0.25 mol of diethylene glycol monomethyl ether per mole of melamine in the starting material. You add the acid mentioned in the examples as a catalyst in the added amount and warmed to 85 ° C. After reducing the Volatile constituents are distilled under a pressure of 15 mbar For an hour and then neutralized with one of the set amount of acid equivalent amount of triethanolamine. At 110 ° C and 15 mbar is distilled for another 15 minutes, if necessary with the specified amount of butyl glycol and diluted to room temperature cooled down. After filtration, clear, colorless or pale yellow colored resins with those given in Table 3 analytical indicators.

Example 21

Who in a reactor with stirrer, cooler and distillation the 460 g of the hexamethoxymethyl melamine resin Cymel 303 with 36 g Diethylene glycol monomethyl ether and 2.80 g of p-toluenesulfonic acid mixes and warmed to 85 ° C. Volatiles are added during one hour at this temperature and a pressure of 25 mbar distilled off. After neutralization with tributylamine, the Distillation continued for a further 15 minutes at 100 ° C. and 25 mbar. After dilution with 35 ml of methoxypropanol and filtration 490 g of a clear, colorless resin with a stoving back stood at 89.8% and a viscosity of 4.3 Pa · s at 23 ° C.

The resin contains 0.3% free methanol, the conversion of diethylene glycol monomethyl ether is 96%.

Example 22

514 g of hexabutoximethylmelamine are mixed with 0.5 mol of tetraethylene gly colmonomethyl ether per mole of melamine and 0.5% by weight of p-toluenesulfone acid added and heated to 90 ° C. At 30 mbar and 90 ° C volatile components and reaction products for 60 minutes distilled off. After neutralization with triethanolamine, white Distilled for 15 minutes at reduced pressure and 110 ° C. Man receives a clear, colorless resin after cooling and filtration with a viscosity of 4.5 Pa · s at 23 ° C in 95% yield.

Example 23

From a mixture of 1.6 moles (based on melamine) of a hexa Butoximethylmelaminharzes with 164 g of diethylene glycol mono butyl ether and 0.5 wt .-% p-toluenesulfonic acid at 90 ° C and 30 mbar volatile constituents and reaction products during 60 Minutes distilled off. Another distillation at 25 mbar and 110 ° C after neutralization with methyldiethanolamine over 15 Minutes. The viscosity of the clear, colorless resin is after Cooling and filtration 4.0 Pa · s.

Comparative Example 2

In analogy to Example 1 in DE-PS 24 14 426 were in one Reactor with stirrer, cooler and distillation receiver 700 g one Hexamethoximethylmelamine in 1520 g ethylene glycol monomethyl ether dissolved, mixed with 28 g of 65% nitric acid and 35 minutes stirred at 35 ° C. After neutralization with 25 g 50% sodium bicarbonate caustic was a pH of 8.5. Within 2.5  The solution was heated at a temperature of 85 ° C and one hour Evaporated pressure from 90 to 130 mbar. For another 30 minutes the pressure was reduced to 30 mbar and the distillation continued set. After filtering off the precipitated sodium nitrate, he 940 g of a colorless, clear resin were held with a viscose 650 mPa · s at 23 ° C. Free methanol could not be replenished be shown, the content of free ethylene glycol monomethyl ether was 15.5%.

General preparation instructions for Examples 24 to 28

468 g of a hexamethoxymethylmelamine resin were mixed with one mole Tetraethylene glycol monomethyl ether per mole of melamine in the HMMM resin and 1.5 mol% of p-toluenesulfonic acid were added. You add the in Table 4 specified amount of the alcohol listed there and heated to 85 ° C. After the temperature is reached, the pressure lowered to 20 mbar, then for 80 minutes volatile constituents are distilled off. After cooling to 60 ° C neutralized with tributylamine, heated to 110 ° C and at reduced decorated pressure distilled for a further 20 minutes. After cooling and Filtration gives clear, colorless resins in yields 95% and with the analytical data given in Table 4.

3. Lacquer formulations General manufacturing instructions for an acid-curing lacquer

70 g Alftalat AR (alkyl resin) 300 (60 percent), 20 g of the in Examples mentioned melamine formaldehyde (MF) resin (95 wt .-%) and 52 g of ethanol / 1-methoxypropanol-2 (2: 1) mixed with a spatula. The paint 12 is used as the hardener Wt .-% p-toluenesulfonic acid (20 percent solution in ethanol) be moved to MF resin. The lacquer so produced is one Solids content of approx. 40% by weight. In the binder mix there is Alftalat AR 300 and melamine resin in a ratio of 7: 3.

General regulation for the production of solvent-based white pigmented stove enamel Pigment paste

1200 g of Kronos RN 57 titanium dioxide pigment, 1000 g of alkyd resin binder Alkydal R 40 (60 percent in xylene) and 200 g Methoxipropanol are rubbed twice on a funnel mill, so that a uniform paste is created.

Lacquer formulation

30 g of the pigment paste described above, 22.5 g of the alkyd resin Alkydal R40 and a 9.0 g solid resin equivalent amount of in the examples listed MF resin with a spatula stirred. Alkydal R40 and MF- Resin in a ratio of 7: 3 and twice as much binder as pigment before (solvent: binder: pigment = 2: 2: 1).

General regulation for the production of a solvent containing clear varnish

From 50 g of an OH group-containing polyacrylate (Luprenal® 240 S) with an OH number of 65 and a solids content of 60% by weight and 20 g melamine resin, based on the solids content in the Examples mentioned melamine resins, and one for a solid content of 50 wt .-% sufficient amount of a hydrocarbon (Solvesso® 100) a clear coat is produced with stirring. For Accelerating the hardening can 0.5% by weight of p-toluenesul fonic acid can be added.  

4. Paint tests

To clarify the application technology advantage of Binder according to the invention or amino resins was used as Ver a standard hexa in each of the paint tests methoximethylmelamine resin (HMMM comparison) like it also partially used as starting material in the previous examples was chosen with the following analytical characteristics:

Solids content: 93-96%
Viscosity (23 ° C): 2000-6000 mPas
free formaldehyde: <0.5%
Methanol, bound: <5 mol / mol melamine
Formaldehyde, bound: <5.5 mol / mol melamine.

In order to ensure comparability, within a Series in each case resins according to the invention and the standard resin under comparable conditions processed and checked.

General stipulation for testing the burn-in reactivity

6 glass plates (90 × 150 × 2 mm) are coated using a 150-µm film frame with the manufactured according to the above regulation th solvent-containing, white pigmented lacquer, which in the contains amino resin mentioned in the following examples and 6 glass plates with an identical varnish, which instead of the invention Amino resin contains the commercially available comparison resin and hardens the paintwork next to each other in a drying cabinet at kon constant temperature. After 10, 20, 30, 40, 50 and 60 min each because a glass plate of comparison and a glass plate of Taken sample and after at least ten minutes cooling the Pendulum hardness determined according to DIN 53157.

General instructions for testing acid hardening (Kempf test)

With the help of a 100 µm film pulling frame, a 380 × is coated 67 × 3 mm glass plate with the manufactured according to the above regulation acid-curing lacquer. After five minutes of storage in a convection oven at 40 ° C and then five minutes The progress of the hardening reaction at room temperature based on the decrease in the stickiness of the surface with an ab Chalk stamp device according to Kempf (supplier: Erichsen GmbH & CoKG, 5870 Hemer-Sundwig / Westf.). It is graded by Ver immediately with a scale (grade 5 = very sticky, grade 0 = sticky  free). The curing and testing cycle is a total of six times carried out.

General regulation for the gradient oven test

The stoving enamel is drawn in with a 200 µm film frame 567 × 90 × 0.75 mm deep-drawn sheet, allows to flash off for 10 minutes and burns in a gradient oven, type 2612, from Byk 30 Mi. grooves over a temperature range of 80 ° C to 180 ° C. After 24- hour storage at 50% rel. Humidity and 23 ° C, will be after successive tests in the individual temperature zones carried out:

• - the layer thickness is determined with a layer thickness measuring device, Type Deltascope, from Fischer 7032 Sindelfingen.
• - The pendulum hardness is determined according to DIN 53157 with a device Type 5840, from Byk.
• - The cross cut test is carried out according to DIN 53151 with a Cross cut knife and scotch tape.
• - The Erichsen cupping is carried out according to DIN 53156 with a device Type 5313, from Byk.
• - The xylene resistance is determined by a 10 minute lay one side of the sheet, standing on the long edge, in a xylene bath, immersion depth approx. 3 cm and then graded with 1 = no change in the paint layer, 0.5 = due to staining zen slight damage with the fingernail, 0 = the paint film can be removed by rubbing with a cloth.

Test results

Using the MF resins listed in Tables 5 and 6 white pigmented, stoving enamels as well as acid-curing paints according to the general manufacturing instructions posed. The pendulum hardness after baking at 150 ° C are in Ta belle 5 stated. The results of acid curing (Kempf tests) are summarized in Table 6.  

Table 5

The high values for the pendulum hardness when using the MF resins from the examples compared to the comparative examples or HMMM illustrate the high reactivity. The increased reactivity at Acid hardening is achieved by quickly reaching a stick documented free film.

Table 6

From the amino resins according to the invention from Examples 24, 27 and 28 and the comparative HMMM resin become acid-curing clear paints and solvent-based, white pigmented paints for the Testing of the stoving reactivity produced and according to the general my regulations for the recording of the hardness curve and for the Acid hardening test processed and tested. The results  thermal curing and acid curing are in the Tables 7 and 8 summarized.

Table 7

Table 8

With the MF resins from Examples 2, 6 and 9 and with one HMMM comparisons were white pigmented, solvent-containing ones Firing lacquers according to the general regulation listed above represents:

The paints thus produced were knife-coated onto deep-drawn sheets and in the gradient oven according to the general instructions burns and tested. The results of the test are in Table 9 and 10 summarized.

The high values for the pendulum hardness at relatively low ones Baking temperatures (Table 9) illustrate the high reactivities as well as achieving a xylene-resistant film Temperatures below 180 ° C (Table 10).

From the amino resin according to the invention from Example 19 and from a HMMM reference resin were made according to the general procedure solvent-based clear coats and an acid-catalyzed solvent medium clearcoat. The varnishes so produced were knife-coated on deep-drawn sheet metal, according to the general procedure Script burned in the gradient oven and checked. The test results are summarized in Tables 11 and 12 show by the rapid increase in the pendulum hardness and the low temperature reached water and xylene resistance the high reactivity of the melamine-formaldehyde according to the invention Resins that can be further increased by acid catalysis.

Table 11

Table 12

a) Measured value not due to insufficient hardening of the paint determinable.

Claims (10)

1. Containing binder

• A) an aminotriazine derivative in which the primary amino groups of triazine are methylolated on average with at least one mole of formaldehyde per mole of primary amino groups and these methylol groups are etherified on average with at least 0.5 mole of primary alcohol per mole of methylol group, and it is in the containing primary alcohols around a mixture
  • a) 0.5-99.5 mol% of a C₁-C₄ alkanol and
  • b) 99.5-0.5 mol% of an alcohol of the formula R¹-O- [R²-O] _n -R³-OH (I), wherein R¹ is a C₁-C₂₄ alkyl group or a C₆-C₁2 aryl group , which may optionally be substituted by one to three C₁-C₄-alkyl groups and, R² and R³ independently of one another represent a C₂-C₄-alkylene group and n is an integer from 1-100, or a mixture of higher-boiling alcohols with a Boiling point above 120 ° C at 1 bar, which contains at least 10 mol%, based on the higher boiling alcohols, alcohols of formula 1, and
• B) a crosslinkable radical polymer, polycondensate or polyadduct crosslinkable with the aminotriazine derivative.

2. Binder according to claim 1, containing a radical Polymer with a hydroxyl number from 20 to 200. 3. Binder according to claim 1 or 2, containing an aqueous Dispersion of components A. 4. Binder according to one of claims 1 to 3, containing a Aminotriazine resin in which the primary amino groups of the Tri azins with at least 1.7 moles of formaldehyde per mole of primary Amino group methyloliert and these methylol groups with mind at least 0.7 moles of primary alcohol are etherified.   5. aminotriazine derivative in which the primary amino groups of the triazine are methylolated on average with at least one mole of formaldehyde per mole of primary amino groups and these methylol groups are etherified on average with at least 0.5 mole of primary alcohol per mole of methylol group, and it is the primary Containing alcohol around a mixture

• a) 50-99.5 mol% of a C₁-C₄ alkanol and
• b) 0.5-50 mol% of an alcohol of the above formula I or a mixture of higher-boiling alcohols with a boiling point above 12 ° C. at 1 bar, which is at least 10 mol%, based on the higher-boiling alcohols, of the formula I contains.

6. aminotriazine derivative according to claim 5, wherein the primary alcohol is a mixture of

• a) 90-99 mol% of a C₁-C₄ alkanol and
• b) 10-1 mol% of an alcohol of formula I or the mixture of higher boiling alcohols.

7. aminotriazine derivative according to claim 5 or 6, which herge was made by transacetalization of aminotriazine derivatives ten, which are etherified only with C₁-C₄ alkanols, with the alcohols b) in the presence of an acid which is in water has a pK value <4 at 25 ° C. 8. aminotriazine derivative according to claim 7, wherein the conversion of Alcohols b) greater than 50%, based on the alcohols b) used. 9. Use of binders according to claims 1 to 4 as a binder medium in paints. 10. Coated with a binder according to claims 1 to 4 Substrates.